TWI619299B - Lithium metal oxide material, the use thereof in a positive electrode of a secondary battery and a method for preparing such a lithium metal oxide material - Google Patents

Lithium metal oxide material, the use thereof in a positive electrode of a secondary battery and a method for preparing such a lithium metal oxide material Download PDF

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TWI619299B
TWI619299B TW105128646A TW105128646A TWI619299B TW I619299 B TWI619299 B TW I619299B TW 105128646 A TW105128646 A TW 105128646A TW 105128646 A TW105128646 A TW 105128646A TW I619299 B TWI619299 B TW I619299B
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metal oxide
lithium metal
oxide material
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夏興
韓宋基
詹斯 保羅森
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烏明克公司
優美科韓國有限責任公司
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Abstract

一種粉末狀鋰金屬氧化物材料，其具有空間群為Fd-3m之立方結構，且具有式Li1-a[(NibMn1-b)1-xTixAy]2+aO4，其中0.005x0.018、0y0.05、0.01a0.03、0.18b0.28，其中A係來自除了Li、Ni、Mn及Ti以外的金屬元素之群組的一或多種元素。 A powdery lithium metal oxide material having a cubic structure of a space group of Fd-3m and having the formula Li 1-a [(Ni b Mn 1-b ) 1-x Ti x A y ] 2+a O 4 , of which 0.005 x 0.018, 0 y 0.05, 0.01 a 0.03, 0.18 b 0.28, wherein A is one or more elements from the group of metal elements other than Li, Ni, Mn, and Ti.

Description

鋰金屬氧化物材料、其於二次電池之正極內的用途、以及製備此鋰金屬氧化物材料之方法 Lithium metal oxide material, use thereof in the positive electrode of a secondary battery, and method of preparing the lithium metal oxide material

本發明係關於一種鋰金屬氧化物材料，具體而言，係關於一種經摻雜基於鋰錳鎳之氧化物、係關於其在一二次電池之一正極中之用途及一種用於製備此鋰金屬氧化物材料之方法。 The present invention relates to a lithium metal oxide material, in particular to a doped lithium manganese nickel based oxide, for its use in a positive electrode of a secondary battery and a method for preparing the lithium A method of metal oxide material.

市售可得的鋰離子電池組一般含有基於石墨(graphite-based)之陽極及陰極材料。陰極材料通常是能可逆地嵌入鋰及脫嵌鋰的粉末狀材料。在現代可充電式電池組LiCoO2(LCO)中，含大約相似量之Ni、Mn、Co之Li1+a(NixMnyCoz)1-aO2(NMC)及LiMn2O4(LMO)係主流陰極材料。在1990年由Sony首先採用LCO作為鋰離子電池組之陰極材料。從此，LCO已變成最廣泛使用的陰極材料。尤其，高電壓LCO商品化後，LCO主宰攜帶式電子 產品(諸如智慧型手機及平板電腦)市場。NMC係在大約2000年被開發出來，以利用Ni及Mn替代Co來取代LCO，此係因為Co金屬價格高。NMC具有相當於LCO的重力能量密度，但是容積能量密度較低，此係因為NMC降低產物密度。現今，NMC主要用於汽車應用，例如電動車(EV)及油電混合車(HEV)。此係因為NMC比LCO更便宜，並且汽車應用需要比攜帶式電子器件低的容積密度。 Commercially available lithium ion batteries typically contain graphite-based anode and cathode materials. The cathode material is typically a powdered material that reversibly intercalates lithium and deintercalates lithium. In the modern rechargeable battery pack LiCoO 2 (LCO), Li 1+a (Ni x Mn y Co z ) 1-a O 2 (NMC) and LiMn 2 O 4 containing approximately a similar amount of Ni, Mn, Co. (LMO) is the mainstream cathode material. In 1990, Sony first adopted LCO as the cathode material for lithium-ion battery packs. Since then, LCO has become the most widely used cathode material. In particular, after the commercialization of high-voltage LCOs, LCO dominates the market for portable electronic products such as smart phones and tablets. The NMC system was developed in about 2000 to replace LCO with Ni and Mn instead of Co because of the high price of Co metal. NMC has a gravitational energy density equivalent to LCO, but the volumetric energy density is lower because NMC reduces product density. Today, NMC is primarily used in automotive applications such as electric vehicles (EVs) and hybrid electric vehicles (HEVs). This is because NMC is less expensive than LCO, and automotive applications require a lower bulk density than portable electronics.

LMO材料自1990年代中期以來已被開發。LMO具有含「3D」Li離子之擴散路徑的尖晶石結構。LMO已廣泛用於各種應用，諸如電動工具、電動腳踏車，及用於汽車應用中。與LCO及NMC相比較，LMO更便宜且具有高Li擴散能力。然而，與LCO及NMC之280mAh/g理論比電容相比較，LMO具有140mAh/g之較低理論比電容。因此，為了改善LMO之重力能量密度，唯一的已知做法係增加操作電壓。 LMO materials have been developed since the mid-1990s. LMO has a spinel structure with a diffusion path of "3D" Li ions. LMO has been used in a variety of applications, such as power tools, electric bicycles, and in automotive applications. Compared to LCO and NMC, LMO is cheaper and has a high Li diffusion capacity. However, compared to the 280 mAh/g theoretical specific capacitance of LCO and NMC, LMO has a lower theoretical specific capacitance of 140 mAh/g. Therefore, in order to improve the gravity energy density of LMO, the only known practice is to increase the operating voltage.

在1995年，Dahn等人揭示一種新化合物LiMn1.5Ni0.5O4，其藉由在LiMn2O4式中用0.5 Ni原子替代0.5 Mn原子而得。經發現，為了使LiMn1.5Ni0.5O4完全脫鋰，應施加4.9V(相對於Li)之充電電壓。LiMn1.5Ni0.5O4具有相似於LiMn2O4之比電容。LiMn1.5Ni0.5O4之晶體結構保持與LiMn2O4相同，因此LiMn1.5Ni0.5O4之速率能力(rate capability)非常良好。然而，歸因於較高操作電壓，與LiMn2O4相比較， LiMn1.5Ni0.5O4之重力能量密度顯著改善。從此，尖晶石型LiMn1.5Ni0.5O4(另稱為「LMNO」)已變成陰極材料研究與開發的重要領域。 In 1995, Dahn et al. revealed a new compound, LiMn 1.5 Ni 0.5 O 4 , which was obtained by substituting 0.5 Ni atoms for 0.5 Mn atoms in LiMn 2 O 4 . It was found that in order to completely delithiate LiMn 1.5 Ni 0.5 O 4 , a charging voltage of 4.9 V (vs. Li) should be applied. LiMn 1.5 Ni 0.5 O 4 has a specific capacitance similar to that of LiMn 2 O 4 . The crystal structure of LiMn 1.5 Ni 0.5 O 4 remains the same as that of LiMn 2 O 4 , so the rate capability of LiMn 1.5 Ni 0.5 O 4 is very good. However, due to the higher operating voltage, the gravitational energy density of LiMn 1.5 Ni 0.5 O 4 is significantly improved compared to LiMn 2 O 4 . Since then, spinel LiMn 1.5 Ni 0.5 O 4 (also known as "LMNO") has become an important field of research and development of cathode materials.

然而，開發LMNO面對數個問題。首先，缺乏用於非常高電壓應用(意指約5V)的良好電解液系統。鋰離子電池組之當前應用著重於低於4.5V之操作電壓，例如，用於大多數智慧型手機之鋰離子電池組操作於4.35V，及用於汽車應用之電池組操作於約4.1V至4.2V。此低操作電壓之主要原因之一與電解液相關。當電壓高於4.5V時，電解液中的當前有機溶劑(主要係線性碳酸鹽及環狀碳酸鹽)開始分解，而形成負面影響陰極/電解液及陽極/電解液界相的副產物。此類副產物劣化電化學電池組效能且造成迅速電容衰退。正在進行改善在大於4.5V電壓下之電解液穩定性的研究。研究方向包括發現新溶劑、發明新鹽、組合功能性添加物等。 However, developing LMNO faces several issues. First, there is a lack of a good electrolyte system for very high voltage applications (meaning about 5V). Current applications for lithium-ion battery packs focus on operating voltages below 4.5V, for example, lithium-ion battery packs for most smartphones operate at 4.35V, and battery packs for automotive applications operate at approximately 4.1V 4.2V. One of the main reasons for this low operating voltage is related to the electrolyte. When the voltage is higher than 4.5 V, the current organic solvents (mainly linear carbonates and cyclic carbonates) in the electrolyte begin to decompose, forming by-products that negatively affect the cathode/electrolyte and anode/electrolyte boundary phases. Such by-products degrade electrochemical cell performance and cause rapid capacitance degradation. Research is being conducted to improve the stability of electrolytes at voltages greater than 4.5V. Research interests include the discovery of new solvents, the discovery of new salts, and the combination of functional additives.

使用LMNO之另一關鍵問題係材料本身的高電壓穩定性問題。當充電至高電壓時，Mn溶解加劇。已溶解之Mn遷移通過電解液且沉積在陽極側上，破壞陽極表面上的固液界相(Solid Electrolyte Interphase(SEI))。在電池組循環期間，Mn持續溶解且破壞此SEI，藉此持續消耗Li以在陽極上形成新SEI。此導致電池組中的迅速鋰損耗及迅速電容衰退。 Another key issue with LMNO is the high voltage stability of the material itself. When charged to a high voltage, Mn dissolution is exacerbated. The dissolved Mn migrates through the electrolyte and deposits on the anode side, destroying the Solid Electrolyte Interphase (SEI) on the surface of the anode. During the battery cycle, Mn continues to dissolve and destroy this SEI, thereby continuing to consume Li to form a new SEI on the anode. This results in rapid lithium loss and rapid capacitance degradation in the battery pack.

因此，本發明之一目的係提供展現循環穩定性、熱穩定性、充電率效能等方面性質改善的LMNO陰 極材料。 Accordingly, it is an object of the present invention to provide an LMNO which exhibits improved properties in terms of cycle stability, thermal stability, and charge rate performance. Extreme material.

從第一態樣觀之，本發明可提供以下產物實施例： Viewed from the first aspect, the present invention provides the following product examples:

實施例1：一種粉末狀鋰金屬氧化物材料，其具有空間群為Fd-3m之立方結構，且具有式Li1-a[(NibMn1-b)1-xTixAy]2+aO4，其中0.005x0.018、0y0.05、0.01a0.03、0.18b0.28，其中A係來自除了Li、Ni、Mn及Ti以外的金屬元素之群組的一或多種元素。需要限制Li/金屬比率(1-a)/(2+a)，以避免雜質形成或效能劣化。太低Li/金屬比率會導致雜質(諸如NiO)形成，而太高Li/金屬比率會導致增加Ni3+/Ni2+之比率，其降低材料之電化學反應性。 Embodiment 1: A powdery lithium metal oxide material having a cubic structure of a space group of Fd-3m and having the formula Li 1-a [(Ni b Mn 1-b ) 1-x Ti x A y ] 2 +a O 4 , of which 0.005 x 0.018, 0 y 0.05, 0.01 a 0.03, 0.18 b 0.28, wherein A is one or more elements from the group of metal elements other than Li, Ni, Mn, and Ti. It is necessary to limit the Li/metal ratio (1-a) / (2+a) to avoid impurity formation or performance degradation. Too low a Li/metal ratio results in the formation of impurities such as NiO, while too high a Li/metal ratio results in an increase in the ratio of Ni 3+ /Ni 2+ which reduces the electrochemical reactivity of the material.

實施例2：根據本發明之鋰金屬氧化物材料，其中0<y，其中A包含Al、Mg、Zr、Cr、V、W、Nb及Ru之一或多者，其中較佳地，A由來自Al、Mg、Zr、Cr、V、W、Nb及Ru之一或多種元素組成。如自上式明白，A係摻雜劑。A摻雜劑(亦稱為摻雜試劑)係(以非常低的濃度)經***物質中以改變該物質的電性質或光學性質的微量雜質元素。 Embodiment 2: A lithium metal oxide material according to the present invention, wherein 0 < y, wherein A comprises one or more of Al, Mg, Zr, Cr, V, W, Nb and Ru, wherein preferably, A is It is composed of one or more elements of Al, Mg, Zr, Cr, V, W, Nb and Ru. As understood from the above formula, A-based dopants. A dopant (also known as a doping agent) is a trace impurity element that is inserted into a substance (at a very low concentration) to alter the electrical or optical properties of the substance.

實施例3：在該鋰金屬氧化物材料中，x0.016。最多至x=0.018之一位準，及更易於最多至x=0.016之一位準，Ti可均勻地摻雜至LMNO之晶體結構 中。當充電至4.9V時，此材料展現改善的循環穩定性、速率能力、安全性質及高電壓穩定性。歸因於改善，此類陰極材料展現對於鋰離子電池組之各種應用的適用可能性，例如，電動工具、電動腳踏車等。 Example 3: In the lithium metal oxide material, x 0.016. Up to a level of x=0.018, and more easily up to one of x=0.016, Ti can be uniformly doped into the crystal structure of the LMNO. When charged to 4.9V, this material exhibits improved cycle stability, rate capability, safety properties, and high voltage stability. Due to improvements, such cathode materials exhibit application possibilities for various applications of lithium ion battery packs, such as power tools, electric bicycles, and the like.

實施例4：在該鋰金屬氧化物材料中，0y0.02且(y/x)<0.5。 Example 4: In the lithium metal oxide material, 0 y 0.02 and (y/x) < 0.5.

實施例5：根據本發明之鋰金屬氧化物材料，其中在使用Cu k-α輻射測定的X光繞射圖中，米勒指標(111)之波峰的半寬高對米勒指標(004)之波峰的半寬高具有至少0.6且至多1之比率。在實施例5中，米勒指標(111)之波峰的半寬高對米勒指標(004)之波峰的半寬高之該比率指示在該材料內部之應變。該比率愈大，在該材料內部之該應變愈低，但是需要一定應變以達成良好電化學效能，而太大的應變指示在該材料內部之不均勻性。 Embodiment 5: A lithium metal oxide material according to the present invention, wherein a half-height of a peak of a Miller index (111) versus a Miller index (004) in an X-ray diffraction diagram measured using Cu k-α radiation The half width of the peak has a ratio of at least 0.6 and at most 1. In Embodiment 5, the ratio of the half width of the peak of the Miller index (111) to the half width of the peak of the Miller index (004) indicates the strain inside the material. The greater the ratio, the lower the strain within the material, but requires some strain to achieve good electrochemical performance, while too much strain indicates non-uniformity within the material.

實施例6：根據本發明之鋰金屬氧化物材料係結晶單相材料。較佳地，該材料具有尖晶石結構。 Example 6: A lithium metal oxide material according to the present invention is a crystalline single phase material. Preferably, the material has a spinel structure.

實施例7：根據本發明之鋰金屬氧化物材料，藉此Ti均勻地分布在該材料之粒子內部。 Example 7: A lithium metal oxide material according to the invention whereby Ti is uniformly distributed inside the particles of the material.

顯而易見，上文所述的個別產物實施例之各者可與在其之前描述之產物實施例之一或多者結合。 It will be apparent that each of the individual product embodiments described above can be combined with one or more of the product embodiments previously described.

從第二態樣觀之，本發明可提供下列用途實施例8：根據本發明之鋰金屬氧化物材料在一二次電池之一正極中之用途。 Viewed from the second aspect, the present invention can provide the following use Example 8: Use of a lithium metal oxide material according to the present invention in a positive electrode of a secondary battery.

從第三態樣觀之，本發明可提供下列方法實 施例： Viewed from the third aspect, the present invention can provide the following methods. Example:

實施例9：一種用於製備根據本發明之粉末狀鋰金屬氧化物材料之方法，該方法包含下列步驟：-提供包含Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之來源之混合物，藉此Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之該等來源的相對量對應該鋰金屬氧化物材料之式；-以第一溫度熱處理該混合物達第一時間期間，藉此該第一溫度係至少900℃，藉以獲得第一熱處理混合物；及-以第二溫度熱處理該第一熱處理混合物達第二時間期間，藉此該第二溫度係至多800℃。尤其，此最後步驟很重要，此係因為最後步驟允許生產相純度(phase purity)較高的材料。較佳地，該第二溫度係介於650℃與750℃之間。此方法導致均勻Ti分布，使得Ti可適當地作為摻雜劑。較佳地，Ti及/或包含在A中之該等元素的該等來源係氧化物。 Embodiment 9: A method for preparing a powdery lithium metal oxide material according to the present invention, the method comprising the steps of: providing an element comprising the Ni, Mn, Li, Ti, and the element contained in A or the elements a mixture of sources whereby the relative amounts of Ni, Mn, Li, Ti, and the elements contained in A or the sources of the elements correspond to the formula of the lithium metal oxide material; - heat treating the first temperature The mixture is for a first time period, whereby the first temperature is at least 900 ° C to obtain a first heat treatment mixture; and - the first heat treatment mixture is heat treated at a second temperature for a second time period, whereby the second temperature system Up to 800 ° C. In particular, this last step is important because the final step allows the production of materials with higher phase purity. Preferably, the second temperature system is between 650 ° C and 750 ° C. This method results in a uniform Ti distribution such that Ti can be suitably used as a dopant. Preferably, Ti and/or the source of the elements contained in A are oxides.

實施例10：在該方法中，Ni及Mn的該等來源由共沉澱之氧基-氫氧化鎳錳或碳酸鎳錳所形成，藉此Ti之該來源係TiO2，且其中在提供包含Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之來源之混合物的該步驟之前，該TiO2塗佈在該共沉澱之氧基-氫氧化鎳錳或碳酸鎳錳上。在特定實施例中，Ti之較佳來源係次微米大小之TiO2粉末，其具有至少8m2/g之BET且由具有d50< 1μm之初級粒子所組成，該等初級粒子係非聚集的。 Example 10: In the method, the sources of Ni and Mn are formed by coprecipitated oxy-nickel hydroxide or nickel carbonate, whereby the source of Ti is TiO 2 and wherein Ni is provided Prior to this step of Mn, Li, Ti, and a mixture of the elements contained in A or the source of the elements, the TiO 2 is coated on the coprecipitated oxy-nickel hydroxide or nickel carbonate. In a particular embodiment, the preferred source of Ti is a submicron sized TiO 2 powder having a BET of at least 8 m 2 /g and consisting of primary particles having a d50 < 1 μm, the primary particles being non-aggregated.

實施例11：在該方法中，該第一溫度係至多1000℃。 Example 11: In the method, the first temperature system is at most 1000 °C.

實施例12：在該方法中，該第一時間期間係介於5小時與15小時之間。 Example 12: In the method, the first time period is between 5 hours and 15 hours.

實施例13：在該方法中，該第二溫度係至少500℃。 Example 13: In the method, the second temperature is at least 500 °C.

實施例14：在該方法中，該第二時間期間係介於2小時與10小時之間。 Example 14: In the method, the second time period is between 2 hours and 10 hours.

本發明進一步提供一種包含根據本發明之鋰金屬氧化物材料之電化學電池。 The invention further provides an electrochemical cell comprising a lithium metal oxide material according to the invention.

此處適當地提及下列先前技術：1) Höweling Andres等人：「Evidence of loss of active lithium in titanium-doped LiNi0.5Mn1.5O4/graphite cells」 (Journal of Power Sources, 274, Nov. 1 2014, pp.1267-1275)；2) N.V.Kosova等人：「Pecularities of structure, morphology, and electrochemistry of the doped 5 V spinel cathode materials LiNi0.5-xMn1.5-yMx+yO4 prepared by mechanochemical way」 (Journal of Solid State Electrochemistry, Sept. 2 2015)；3) US2015/090926 A1；4) J-H Kim等人：「Effect of Ti substitution for Mn on the structure of LiNi0.5Mn1.5-xTixO4 and their electrochemical properties as Lithium Insertion Material」 (Journal of the Electrochemcial Society, 151, N°11, Oct. 22 2004, page A1911)；5) M Lin等人：「JES Focus issue on intercalation compounds for rechargeable batteries, A strategy to improve cyclic performance of LiNi0.5Mn1.5O4 in a wide voltage region by Ti-doping」 (Journal of the Electrochemcial Society, March 2 2013, pp. 3036-3040)。 The following prior art is appropriately mentioned here: 1) Höweling Andres et al.: "Evidence of loss of active lithium in titanium-doped LiNi 0.5 Mn 1.5 O 4 /graphite cells" (Journal of Power Sources, 274, Nov. 1 2014) , pp.1267-1275); 2) NVKosova et al.: "Pecularities of structure, morphology, and electrochemistry of the doped 5 V spinel cathode materials LiNi 0.5-x Mn 1.5-y M x+y O 4 prepared by mechanochemical way" (Journal of Solid State Electrochemistry, Sept. 2 2015); 3) US2015/090926 A1; 4) JH Kim et al.: "Effect of Ti substitution for Mn on the structure of LiNi 0.5 Mn 1.5 - x Ti x O 4 and their Electrochemical properties as Lithium Insertion Material" (Journal of the Electrochemcial Society, 151, N°11, Oct. 22 2004, page A1911); 5) M Lin et al.: "JES Focus issue on intercalation compounds for rechargeable batteries, A strategy to Improve cyclic performance of LiNi 0.5 Mn 1.5 O 4 in a wide voltage region by Ti-doping" (Journal of the Electrochemcial Society, March 2 2013, Pp. 3036-3040).

與這些文件相反，在本發明中，Li對金屬比率及Ti含量經選擇，以保證經Ti均勻摻雜、係純相、並具有Fd-3m空間群之尖晶石結構，且因此獲得電化學性質之改善。 In contrast to these documents, in the present invention, Li to metal ratio and Ti content are selected to ensure uniform doping of Ti, a pure phase, and a spinel structure of the Fd-3m space group, and thus electrochemically obtained Improvement in nature.

圖1：根據本發明之材料之X光繞射(XRD)圖譜，含米勒指標之指示；圖2：根據本發明之材料及非根據本發明之材料的示差掃描熱析法(DSC)曲線。 Figure 1: X-ray diffraction (XRD) pattern of a material according to the invention, including an indication of the Miller indicator; Figure 2: Differential scanning calorimetry (DSC) curve of a material according to the invention and a material not according to the invention .

作者已發現含有Ti作為摻雜劑的LMNO陰極粉末當在Li離子電池組中使用時具有優異特性。存在Ti 摻雜可有助於改善循環穩定性、速率能力、熱穩定性及高電壓穩定性，其有助於促進LMNO材料之實務應用。可選地，除Ti外的額外摻雜元素可存在。 The authors have found that LMNO cathode powders containing Ti as a dopant have excellent properties when used in Li-ion batteries. Ti exists Doping can help improve cycle stability, rate capability, thermal stability, and high voltage stability, which can help promote the practical application of LMNO materials. Alternatively, additional doping elements other than Ti may be present.

使用下列表徵程序： Use the following characterization procedures:

X光繞射(XRD) X-ray diffraction (XRD)

使用配備有Cu(K-α)靶X光管及繞射光束單光儀之Rigaku D/MAX 2200 PC繞射計在室溫下在15至70之2 Θ度範圍內進行X光繞射。從X光繞射圖譜使用全圖譜匹配及裏特沃爾德精算法(Rietveld refinement method)計算不同相之晶格參數。使用來自Rigaku Corp之稱為「peak search」之軟體且消除K-α 2繞射，計算經選擇之波峰的半寬高(FWHM)。 X-ray diffraction was performed at room temperature in the range of 15 to 70 Torr using a Rigaku D/MAX 2200 PC diffractometer equipped with a Cu (K-α) target X-ray tube and a diffracted beam singlet. From the X-ray diffraction pattern, the full-spectrum matching and the Rietveld refinement method are used to calculate the lattice parameters of the different phases. The half width (FWHM) of the selected peak is calculated using a software called "peak search" from Rigaku Corp. and eliminating K-α 2 diffraction.

鈕釦型電池測試 Button battery test

藉由將一Celgard分隔件放置於受測試之一正極與作為一負極的一片鋰金屬之間，並且於分隔件與電極之間使用在EC/DMC(1：2)中之1M LiPF6之電解液來組裝半電池(鈕釦型電池)。如下製成該正極：以90：5：5之質量比率混合陰極材料粉末、PVDF及炭黑。添加充分的NMP並混合以獲得漿料。藉由市售的電極塗佈器施加該漿料至Al箔。接著，在空氣中以120℃乾燥該電極以移除NMP。該電極之目標載重量係10mg陰極材料/cm2。接著，該經乾燥電極被衝壓以獲得1.8g/cc之電極密度，並 且在組裝鈕釦型電池前，在真空中以120℃再次乾燥。 By placing a Celgard separator between one of the positive electrodes tested and a piece of lithium metal as a negative electrode, and using 1M LiPF 6 in EC/DMC (1:2) between the separator and the electrode Liquid to assemble a half-cell (button battery). The positive electrode was prepared by mixing a cathode material powder, PVDF, and carbon black at a mass ratio of 90:5:5. Sufficient NMP was added and mixed to obtain a slurry. The slurry was applied to the Al foil by a commercially available electrode applicator. Next, the electrode was dried at 120 ° C in air to remove NMP. The target loading capacity of the electrode was 10 mg cathode material / cm 2 . Next, the dried electrode was punched to obtain an electrode density of 1.8 g/cc, and dried again at 120 ° C in a vacuum before assembling the button type battery.

使用表1展示之程序執行本發明中的所有鈕釦型電池測試，其中1C速率定義為160mAh/g。「E-Curr」及「V」分別表示終止電流(end current)與截止電壓(cut-off voltage)。在第一次循環時，測定DQ0.1C(第一次循環之放電容量，速率為0.1C)與IRRQ(不可逆容量)。自循環編號7至編號60獲得循環穩定性之效能。0.1C之電容衰退表示為「Qfade0.1C」。用DQ7及DQ34分別指循環編號7及循環編號34之放電電容，藉由下式計算Qfade0.1C：Qfade0.1C=(1-(DQ34/DQ7))/27*100*100(以每100循環%為單位)。1C之電容衰退表示為「Qfade1C」。用DQ8及DQ35分別指循環編號8及循環編號35之放電電容，藉由下式計算Qfade1C：Qfade1C=(1-(DQ35/DQ8))/27*100*100。1C/1C(1C充電及1C放電)之電容衰退表示為「Qfade1C/1C」。用DQ36及DQ60分別指循環編號36及循環編號60之放電電容，藉由下式計算Qfade1C/1C：(1-(DQ60/DQ36))/24。 All button type battery tests in the present invention were performed using the procedure shown in Table 1, where the 1 C rate was defined as 160 mAh/g. "E-Curr" and "V" indicate the end current and the cut-off voltage, respectively. At the first cycle, DQ0.1C (discharge capacity at the first cycle, rate of 0.1 C) and IRRQ (irreversible capacity) were measured. The performance of the cycle stability is obtained from Cycle No. 7 to No. 60. The capacitance decay of 0.1C is expressed as "Qfade0.1C". Use DQ7 and DQ34 to refer to the discharge capacitors of cycle number 7 and cycle number 34, respectively, and calculate Qfade0.1C by the following formula: Qfade0.1C=(1-(DQ34/DQ7))/27*100*100 (in per 100 cycles) % is the unit). The 1C capacitor decay is expressed as "Qfade1C". Use DQ8 and DQ35 to refer to the discharge capacitor of cycle number 8 and cycle number 35, respectively, and calculate Qfade1C by the following formula: Qfade1C=(1-(DQ35/DQ8))/27*100*100. 1C/1C (1C charging and 1C) The capacitance decay of discharge is expressed as "Qfade1C/1C". DQ36 and DQ60 are referred to as discharge capacitors of cycle number 36 and cycle number 60, respectively, and Qfade1C/1C is calculated by the following equation: (1-(DQ60/DQ36))/24.

浮動充電方法 Floating charging method

在可購得之「3M電池組電解質HQ-115」的最新技術報告中，浮動充電方法被用來測試新型電解質在高電壓的穩定性。該方法是藉由使LCO/石墨袋式電池(pouch cell)或18650電池在4.2V及60℃下連續充電900小時而進行。比較充電之下所記錄的電流。較高的電流反映出發生了更多副反應，因此這種方法能夠識別出在高電壓下電池組中發生的寄生反應。在「Energy Environ.Sci.,6,1806(2013)」中，類似的浮動充電方法用於評估在從5V及高達6.3V相對於Li金屬的高電壓下電解質對抗氧化的穩定性。 In the latest technical report of the commercially available "3M Battery Electrolyte HQ-115", the floating charging method was used to test the stability of the new electrolyte at high voltage. The method was carried out by continuously charging an LCO/graphite pouch cell or 18650 battery at 4.2 V and 60 ° C for 900 hours. Compare the current recorded under charging. Higher currents reflect more side reactions, so this method can identify parasitic reactions that occur in the battery at high voltages. In "Energy Environ. Sci., 6, 1806 (2013)", a similar floating charging method was used to evaluate the stability of the electrolyte against oxidation at a high voltage from 5 V and up to 6.3 V with respect to Li metal.

基於上文知識，藉由針對所需的充電電壓選 擇相對穩定的電解質及陽極材料，可使用浮動充電方法來研究陰極材料在高電壓下的穩定性，其中可藉由漏電流反映來自陰極材料之金屬溶解。 Based on the above knowledge, by selecting the required charging voltage A relatively stable electrolyte and anode material can be used to study the stability of the cathode material at high voltages using a floating charging method in which metal leakage from the cathode material can be reflected by leakage current.

此外，在「Nature Comm.,4,2437(2013)」中，自鋰錳氧化物陰極溶解的錳以金屬或金屬合金之形式沉積於陽極表面上，而沉積量可藉由感應耦合電漿-原子吸收光譜法(ICP-AAS)檢測。這種對陽極的ICP實驗亦可用於研究基於LMNO(經摻雜或未經摻雜)之金屬溶解難題。 Further, in "Nature Comm., 4, 2437 (2013)", manganese dissolved from a lithium manganese oxide cathode is deposited on the surface of the anode in the form of a metal or a metal alloy, and the deposition amount can be obtained by inductively coupling plasma - Atomic Absorption Spectroscopy (ICP-AAS) detection. This ICP experiment on the anode can also be used to study metal dissolution problems based on LMNO (doped or undoped).

因此，與ICP量測相關聯的浮動充電方法(以下稱為「浮動實驗(floating experiment)」)是評估基於LMNO之陰極材料在高電壓及高溫下的副反應及金屬溶解的可行方法。對於實例及相對實例，進行浮動實驗以評估陰極材料在高電壓充電下及在高溫(50℃)下的穩定性。 Therefore, the floating charging method associated with ICP measurement (hereinafter referred to as "floating experiment") is a feasible method for evaluating side reactions and metal dissolution of LMNO-based cathode materials at high voltages and temperatures. For the examples and relative examples, a floating experiment was performed to evaluate the stability of the cathode material under high voltage charging and at high temperatures (50 ° C).

所測試的電池組態是鈕釦型電池，鈕釦型電池係組裝如下：兩個分隔件(來自SK Innovation)位於正極與負石墨電極(Mitsubishi MPG)之間。電解質係於EC/DM(1：2體積比)溶劑中之1M LiPF6。對所製備的鈕釦型電池進行下列充電方案：首先，在恆定電流模式下以C/20速率遞減電流(C/20 rate taper current)將鈕釦型電池充電至一經定義之上限電壓(4.85V相對於石墨)，且接著在50℃下保持在恆定4.85V電壓達144小時。接著，自這些144小時期間累積的電荷及該陰極材料質量計算浮 動容量。此程序後，組裝鈕釦型電池。藉由ICP-OES分析陽極及與陽極接觸的分隔件，判定其等之Mn含量，指示在浮動實驗期間Mn已溶解。 The battery configuration tested was a button-type battery, and the button-type battery was assembled as follows: Two separators (from SK Innovation) were placed between the positive and negative graphite electrodes (Mitsubishi MPG). The electrolyte was attached to 1 M LiPF 6 in an EC/DM (1:2 by volume) solvent. The following charging scheme was performed on the prepared button type battery: first, the button type battery was charged to a defined upper limit voltage (4.85 V) at a C/20 rate taper current in a constant current mode. Relative to graphite), and then maintained at a constant voltage of 4.85 V for 144 hours at 50 °C. Next, the floating capacity was calculated from the charge accumulated during these 144 hours and the mass of the cathode material. After this procedure, assemble the button type battery. The anode and the separator in contact with the anode were analyzed by ICP-OES to determine the Mn content of the anode, indicating that Mn had dissolved during the floating experiment.

DSC測量 DSC measurement

示差掃描熱析法(DSC)係藉由下述執行：首先如上文所述製成鈕釦型電池且以C/25恆定電流將鈕釦型電池充電至4.9V(相對於Li)。接著，鈕釦型電池保持在4.9V且結束條件為電流減小至C/50。接著，拆解鈕釦型電池且取出陰極電極。用碳酸二甲酯(DMC)清洗陰極電極兩次以移除殘餘電解液，且在真空中以120℃乾燥達10分鐘。自電極打出一5mm直徑圓形樣本作為用於DSC測量之樣本，其中添加約30重量%之電解液且使用一封閉DSC電池。TA DSC Q10儀器用於進行DSC測試。測試之溫度範圍係自50℃至350℃，使用0.5℃/min之升溫。最終，報告放熱反應之起始溫度及產生之總熱量。其等指示陰極在電池組中使用時之穩定性。 Differential Scanning Thermal Analysis (DSC) was performed by first making a button type battery as described above and charging the button type battery to 4.9 V (vs. Li) at a C/25 constant current. Next, the button type battery was maintained at 4.9 V and the end condition was that the current was reduced to C/50. Next, the button type battery is disassembled and the cathode electrode is taken out. The cathode electrode was washed twice with dimethyl carbonate (DMC) to remove residual electrolyte, and dried at 120 ° C for 10 minutes in a vacuum. A 5 mm diameter circular sample was punched from the electrode as a sample for DSC measurement, in which about 30% by weight of electrolyte was added and a closed DSC battery was used. The TA DSC Q10 instrument is used for DSC testing. The temperature range tested was from 50 ° C to 350 ° C, using a temperature rise of 0.5 ° C / min. Finally, the onset temperature of the exothermic reaction and the total heat generated are reported. They indicate the stability of the cathode when used in a battery pack.

本發明進一步於下列實例中闡釋：藉由以下處理步驟製造實例1：將NiSO4‧6H2O及MnSO4‧1H2O溶解於水中至110g/L之經加總之總金屬濃度，且具有0.21/0.79之Ni/Mn莫耳比。藉由用水稀釋濃縮氨溶液以到達所欲濃度，來製備含227g/L之NH3濃度之氨溶液。使用水性奈米粒TiO2懸浮液(385g/L)作為摻雜劑進料且NaOH溶液之濃度係400g/L。首先用水及氨 (氨濃度15g/L)充填反應器，且接著加熱最多至60℃。接著，在N2氛圍下，透過控制質量流控制器(MFC)，藉由持續添加Ni-Mn硫酸鹽溶液、氨溶液、TiO2懸浮液及NaOH溶液至連續攪拌槽反應器(CSTR)中，使經Ti摻雜之金屬氫氧化物沉澱。藉由變更NaOH溶液之流速來控制沉澱物程序以到達所欲粒徑，同時Ni-Mn硫酸鹽溶液、氨溶液及TiO2懸浮液之流速保持恆定。前驅物之粒徑到達目標後，NaOH溶液之流速固定。收集所得溢流漿料，並且藉由過濾與上清液分離。用水清洗後，在N2氛圍下，在對流烤箱中以150℃使沉澱之固體乾燥。 The invention is further illustrated in the following examples: Example 1 was prepared by the following processing steps: dissolving NiSO 4 ‧6H 2 O and MnSO 4 ‧1H 2 O in water to a total metal concentration of 110 g/L, with 0.21 Ni/Mn molar ratio of /0.79. An ammonia solution containing a concentration of 227 g/L of NH 3 was prepared by diluting the concentrated ammonia solution with water to reach a desired concentration. A water-based nanoparticle TiO 2 suspension (385 g/L) was used as a dopant feed and the concentration of the NaOH solution was 400 g/L. The reactor was first filled with water and ammonia (ammonia concentration 15 g/L) and then heated up to 60 °C. Next, in a N 2 atmosphere, by continuously controlling the mass flow controller (MFC), by continuously adding a Ni-Mn sulfate solution, an ammonia solution, a TiO 2 suspension, and a NaOH solution to the continuous stirred tank reactor (CSTR), The Ti-doped metal hydroxide is precipitated. The precipitation procedure was controlled to achieve the desired particle size by varying the flow rate of the NaOH solution while the flow rates of the Ni-Mn sulfate solution, the ammonia solution, and the TiO 2 suspension were kept constant. After the particle size of the precursor reaches the target, the flow rate of the NaOH solution is fixed. The resulting overflow slurry was collected and separated from the supernatant by filtration. After washing with water, the precipitated solid was dried at 150 ° C in a convection oven under N 2 atmosphere.

化學分析所獲得之前驅物材料確認與[Ni0.21Mn0.79]0.985Ti0.015金屬原子比率一致之組成物。氧及氫位準指示產物為混合之金屬氧基氫氧化物，SEM攝影展現1μm至15μm且內嵌細TiO2粒子之粒子。藉由乾粉末混合程序，於垂直單軸混合器中均勻地摻合碳酸鋰及所獲得經TiO2塗佈之氧基-氫氧化鎳錳前驅物。訂定摻合比率目標以獲得關於元素Li、Ni、Mn及Ti的下列組成物：Li0.988[(Ni0.21Mn0.79)0.985Ti0.015]2.012，其藉由ICP驗證。Ti均勻分布於粉末中，如可易於驗證。 The composition obtained by chemical analysis confirmed the composition of [Ni 0.21 Mn 0.79 ] 0.985 Ti 0.015 metal atomic ratio. The oxygen and hydrogen levels indicate that the product is a mixed metal oxyhydroxide, and SEM photography reveals particles of 1 μm to 15 μm in which fine TiO 2 particles are embedded. By dry powder mixing procedure, to a vertical uniaxial mixer and evenly blended lithium carbonate coated TiO 2 was obtained by the group - manganese nickel hydroxide precursor. The blend ratio target was set to obtain the following composition for the elements Li, Ni, Mn, and Ti: Li 0.988 [(Ni 0.21 Mn 0.79 ) 0.985 Ti 0.015 ] 2.012 , which was verified by ICP. Ti is evenly distributed in the powder, as can be easily verified.

於箱形爐中以980℃溫度熱處理所獲得之粉末混合物達10小時。接著使溫度降低至700℃達5小時之期間。在這兩個階段中，乾空氣流動通過該箱形爐，使得建置氧化氛圍。產物冷卻至室溫且碾磨成D50=14μm之粒徑分布。最終獲得之材料係 Li0.988[(Ni0.21Mn0.79)0.985Ti0.015]2.012O4。圖1展示實例1之X光繞射(XRD)圖譜，其對應具有空間群Fd-3m之結晶單相立方尖晶石結構。 The obtained powder mixture was heat-treated at a temperature of 980 ° C in a box furnace for 10 hours. The temperature was then lowered to 700 ° C for a period of 5 hours. In both stages, dry air flows through the box furnace, allowing an oxidizing atmosphere to be built. The product was cooled to room temperature and ground to a particle size of D 50 = 14μm distribution. The material finally obtained was Li 0.988 [(Ni 0.21 Mn 0.79 ) 0.985 Ti 0.015 ] 2.012 O 4 . 1 shows an X-ray diffraction (XRD) pattern of Example 1, which corresponds to a crystalline single-phase cubic spinel structure having a space group Fd-3m.

實例2 Example 2

藉由與實例1相同之方法製造實例2，差異在於Li對其他元素之比率經變更而導致下列組成物之材料：Li0.971[(Ni0.21Mn0.79)0.985Ti0.015]2.029O4。 Example 2 was produced by the same method as Example 1, except that the ratio of Li to other elements was changed to result in a material of the following composition: Li 0.971 [(Ni 0.21 Mn 0.79 ) 0.985 Ti 0.015 ] 2.029 O 4 .

相對實例1 Relative example 1

藉由以下處理步驟製造相對實例1：藉由乾粉末混合，於垂直單軸混合器中均勻地摻合碳酸鋰及氧基-氫氧化鎳錳。訂定整體組成目標以獲得關於元素Li、Ni及Mn的下列組成物：Li0.988[Ni0.21Mn0.79]2.012，其藉由ICP驗證。對此摻合物進行與實例1相同之熱處理及碾磨處理。 Comparative Example 1 was made by the following processing steps: lithium carbonate and oxy-nickel hydroxide were uniformly blended in a vertical uniaxial mixer by dry powder mixing. The overall composition target was set to obtain the following composition for the elements Li, Ni, and Mn: Li 0.988 [Ni 0.21 Mn 0.79 ] 2.012 , which was verified by ICP. This blend was subjected to the same heat treatment and milling treatment as in Example 1.

相對實例2 Relative example 2

藉由與實例2相同之方法製造相對實例2，差異在於Li對其他元素之比率經變更而導致下列組成物之材料：Li0.971[(Ni0.21Mn0.79)0.98Ti0.020]2.029O4，其具有之Ti含量超出本發明之範圍。 Comparative Example 2 was produced by the same method as in Example 2, except that the ratio of Li to other elements was changed to result in a material of the following composition: Li 0.971 [(Ni 0.21 Mn 0.79 ) 0.98 Ti 0.020 ] 2.029 O 4 , which has The Ti content is outside the scope of the present invention.

實例1及實例2以及相對實例1進行上述表徵，相對實例2僅進行XRD及鈕釦型電池測量，且獲得 下列結果：表2歸納FWHM(111)/FWHM(004)之比率，及表3歸納當鈕釦型電池充電至4.9V時的鈕釦型電池效能。 Example 1 and Example 2 and Comparative Example 1 were subjected to the above characterization, and only Example 2 was subjected to XRD and button type battery measurement, and the following results were obtained: Table 2 summarizes the ratio of FWHM (111) / FWHM (004) , and Table 3 summarizes Button-type battery performance when the button type battery is charged to 4.9V.

與相對實例1及相對實例2相比較，實例1及實例2展現改善的循環穩定性，尤其自低出許多之Qfade值而清楚可知。 Compared to Comparative Example 1 and Comparative Example 2, Examples 1 and 2 exhibited improved cycle stability, especially from the low Qfade values.

圖2展示實例及相對實例1之DSC曲線，其中空心圓形指示實例1，空心三角形指示實例2，及實心方形指示相對實例1。表4給出來自DSC曲線的起始溫度及積分熱。 2 shows an example and a DSC curve relative to Example 1, wherein a hollow circle indicates Example 1, a hollow triangle indicates Example 2, and a solid square indicates relative Example 1. Table 4 gives the starting temperature and integral heat from the DSC curve.

實例1及實例2之放熱峰具有較高起始溫度，且其等之總熱值小於相對實例1之總熱值。總體而言，此意指與相對實例1相比較，實例1及實例2展現改善之熱穩定性，其與使用此類陰極材料改善實際電池之安全相關。 The exothermic peaks of Examples 1 and 2 have a higher onset temperature and their total calorific value is less than the total calorific value relative to Example 1. Overall, this means that Example 1 and Example 2 exhibited improved thermal stability compared to Comparative Example 1, which was associated with the use of such cathode materials to improve the safety of actual batteries.

表5展示浮動實驗結果。與相對實例1相比較，實例1及實例2展現顯著較低浮動容量及Mn溶解。此指示與相對實例1相比較，實例1及實例2之高電壓穩定性更佳。 Table 5 shows the results of the floating experiments. Example 1 and Example 2 exhibited significantly lower float capacity and Mn dissolution compared to Comparative Example 1. This indication is superior to Comparative Example 1 in that the high voltage stability of Examples 1 and 2 is better.

Claims (14)

一種粉末狀鋰金屬氧化物材料，其具有空間群為Fd-3m之立方結構，且具有式Li1-a[(NibMn1-b)1-xTixAy]2+aO4，其中0.005x0.018、0y0.05、0.01a0.03、0.18b0.28，其中A係來自除了Li、Ni、Mn及Ti以外的金屬元素之群組的一或多種元素。A powdery lithium metal oxide material having a cubic structure of a space group of Fd-3m and having the formula Li 1-a [(Ni b Mn 1-b ) 1-x Ti x A y ] 2+a O 4 , of which 0.005 x 0.018, 0 y 0.05, 0.01 a 0.03, 0.18 b 0.28, wherein A is one or more elements from the group of metal elements other than Li, Ni, Mn, and Ti. 如請求項1之鋰金屬氧化物材料，其中y>0，其中A包含Al、Mg、Zr、Cr、V、W、Nb及Ru之一或多者。A lithium metal oxide material according to claim 1, wherein y > 0, wherein A comprises one or more of Al, Mg, Zr, Cr, V, W, Nb and Ru. 如請求項1之鋰金屬氧化物材料，其中0.005x0.016。Lithium metal oxide material as claimed in claim 1, wherein 0.005 x 0.016. 如請求項1之鋰金屬氧化物材料，其中0y0.02且(y/x)<0.5。A lithium metal oxide material as claimed in claim 1, wherein y 0.02 and (y/x) < 0.5. 如請求項1之鋰金屬氧化物材料，其中在使用Cu k-α輻射測定的X光繞射圖中，米勒指標(111)之波峰的半寬高對米勒指標(004)之波峰的半寬高具有至少0.6且至多1之比率。The lithium metal oxide material of claim 1, wherein in the X-ray diffraction pattern measured by Cu k-α radiation, the half-width of the peak of the Miller index (111) is the peak of the Miller index (004). The half width has a ratio of at least 0.6 and at most 1. 如請求項1之鋰金屬氧化物材料，藉此該鋰金屬氧化物材料係結晶單相材料。The lithium metal oxide material of claim 1, whereby the lithium metal oxide material is a crystalline single phase material. 如請求項1之鋰金屬氧化物材料，藉此Ti均勻地分布在該材料之粒子內部。The lithium metal oxide material of claim 1, wherein Ti is uniformly distributed inside the particles of the material. 一種如請求項1之鋰金屬氧化物材料在一二次電池之一正極中之用途。A use of the lithium metal oxide material of claim 1 in a positive electrode of a secondary battery. 一種用於製備如請求項1之粉末狀鋰金屬氧化物材料之方法，該方法包含下列步驟：- 提供包含Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之來源之混合物，藉此Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之該等來源的相對量對應該鋰金屬氧化物材料之式；- 以第一溫度熱處理該混合物達第一時間期間，藉此該第一溫度係至少900℃，藉以獲得第一熱處理混合物；及- 以第二溫度熱處理該第一熱處理混合物達第二時間期間，藉此該第二溫度係至多800℃。A method for preparing a powdered lithium metal oxide material according to claim 1, the method comprising the steps of: - providing a source comprising Ni, Mn, Li, Ti, and the element contained in A or the source of the elements a mixture whereby Ni, Mn, Li, Ti, and the relative amounts of the elements or elements of the elements contained in A correspond to the formula of the lithium metal oxide material; - heat treating the mixture at a first temperature The first temperature is at least 900 ° C for a period of time to obtain a first heat treatment mixture; and - the first heat treatment mixture is heat treated at a second temperature for a second time period, whereby the second temperature system is at most 800 ° C . 如請求項9之方法，其中Ni及Mn的該等來源由共沉澱之氧基-氫氧化鎳錳或碳酸鎳錳所形成，藉此Ti之該來源係TiO2，且其中在提供包含Ni、Mn、Li、Ti及包含在A中之該元素或該等元素之來源之混合物的該步驟之前，該TiO2塗佈在該共沉澱之氧基-氫氧化鎳錳或碳酸鎳錳上。The method of claim 9, wherein the sources of Ni and Mn are formed from a coprecipitated oxy-nickel hydroxide or nickel manganese carbonate, whereby the source of Ti is TiO 2 , and wherein Ni is provided, Prior to this step of Mn, Li, Ti, and the element comprising the element in A or a source of such elements, the TiO 2 is coated on the coprecipitated oxy-nickel hydroxide or nickel carbonate. 如請求項9之方法，其中該第一溫度係至多1000℃。The method of claim 9, wherein the first temperature is at most 1000 °C. 如請求項9之方法，其中該第一時間期間係介於5小時與15小時之間。The method of claim 9, wherein the first time period is between 5 hours and 15 hours. 如請求項9之方法，其中該第二溫度係至少500℃。The method of claim 9, wherein the second temperature is at least 500 °C. 如請求項9之方法，其中該第二時間期間係介於2小時與10小時之間。The method of claim 9, wherein the second time period is between 2 hours and 10 hours.
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